Fungicidal compositions containing N-acetonylbenzamides

ABSTRACT

The present invention relates to fungicidal compositions and their use as a method for controlling phytopathogenic fungi comprising the application of a selected fungicidally active N-acetonylbenzamide compound and a second fungicidally active compound selected from the group consisting of an inhibitor of respiration at cytochrome complex III, ziram, fluazinam, zarilamide, chlorothalonil, propamocarb, folpet, fosetyl-aluminum or a fungitoxic metabolite thereof, a triphenyltin type fungicide and a copper containing fungicide to plant seed, to plant foliage or to a plant growth medium. The compositions and method of use provide higher fungicidal activity than separate use of the same compounds.

This is a continuation-in-part application of Ser. No. 09/433,676, filedNov. 4, 1999 (now U.S. Pat. No. 6,075,047, Jun. 13, 2000) which is adivisional application of Ser. No. 09/148,604, filed Sep. 4, 1998 (nowU.S. Pat. No. 6,004,947, Dec. 21, 1999) which claims for domesticpriority 60/072,725 filed Jan. 27, 1998.

The present invention relates to new fungicidal compositions and theiruse as a method for controlling phytopathogenic fungi on plants.

It is always desirable to improve products which can be used by growersin order to combat fungal diseases of crops, and in particular diseasescaused by fungi in the class Oomycetes.

It is also always desirable to reduce the doses of chemical productsspread into the environment to combat fungal attacks on crops inparticular by reducing the application doses of the products.

It is also always desirable to increase the number of antifungalproducts available to growers in order that they will find, among theseproducts, the one which is best suited to the grower's specific use.

One objective of the invention is thus to provide novel fungicidalcompositions which are useful against the problems outlined above.

Another objective of the invention is to propose novel fungicidalcompositions which are useful in the preventive and curative treatmentof diseases caused by fungi of the class Oomycetes.

Still another objective of the invention is to propose novel fungicidalcompositions which are of improved efficacy against mildew and/or lateblight caused by Oomycetes.

Yet another objective of the invention is to propose novel fungicidalcompositions which are of improved efficacy against downy mildew ingrapes and other crops and/or late blight in tomatoes and potatoes.

It has now been found that these objectives may be achieved, partly ortotally, by means of the fungicidal compositions according to thepresent invention.

U.S. Pat. Nos. 5,304,572 and 5,677,333 disclose applying mixtures of theN-acetonylbenzamides disclosed therein with other fungicidal compounds.It has now been discovered that application of the N-acetonylbenzamidesdisclosed in these patents in combination with selected other fungicidalcompounds provides unexpectedly high fungicidal activity and iseffective in controlling phytopathogenic fungi at lowerN-acetonylbenzamide dosage rates than those disclosed in the U.S. Pat.No. 5,304,572. Although U.S. Pat. No. 5,677,333 discloses the use ofN-acetonylbenzamides in combination with ethylene bisdithiocarbamates,cymoxanil and dimethomorph to provide unexpectedly high fungicidalactivity, the synergistic combinations of this invention are notdisclosed or suggested in that patent.

In a first embodiment of this invention, there is provided a compositioncomprising

(a) a fungicidally effective amount of a first fungicidally activecompound having the formula (I)

or an agronomically acceptable salt thereof wherein

R¹ and R³ are each independently halo or (C₁-C₄)alkyl,

R² is (C₁-C₄)alkyl, (C₂-C₄)alkenyl, (C₂-C₆)alkynyl, (C₁-C₄)alkoxy orcyano,

R⁴ and R⁵ are each independently a hydrogen atom or (C₁-C₄)alkyl,provided that at least one of R⁴ and R⁵ is (C₂-C₄)alkyl and

X is halo, thiocyano or isothiocyano;

(b) a fungicidally effective amount of a second fungicidally activecompound selected from the group consisting of

(i) an inhibitor of respiration at cytochrome complex III, such as amethoxyacrylate type fungicide, for example, azoxystrobin andkresoxim-methyl,

(ii) ziram

(iii) fluazinam

(iv) zarilamide

(v) chlorothalonil

(vi) propamocarb

(vii) folpet

(viii) fosetyl-aluminum or a fungitoxic metabolite thereof such asphosphorous acid,

(ix) a triphenyltin type fungicide such as fentin hydroxide and fentinacetate and

(x) a copper containing fungicide such as copper(I) sulfate, copper(II)sulfate, copper(II) sulfate pentahydrate, copper(I) oxide, copperhydroxide and Bordeaux mixture; and

(c) an agronomically acceptable carrier.

In a second embodiment of this invention, there is provided a method forcontrolling phytopathogenic fungi on a plant comprising the applicationof

(a) a fungicidally effective amount of a first fungicidally activecompound having the formula (I)

or an agronomically acceptable salt thereof wherein

R¹ and R³ are each independently halo or (C₁-C₄)alkyl,

R² is (C₁-C₄)alkyl, (C₂-C₄)alkenyl, (C₂-C₆)alkynyl, (C₁-C₄)alkoxy orcyano,

R⁴ and R⁵ are each independently a hydrogen atom or (C₁-C₄)alkyl,provided that at least one of R⁴ and R⁵ is (C₂-C₄)alkyl and

X is halo, thiocyano or isothiocyano;

(b) a fungicidally effective amount of a second fungicidally activecompound selected from the group consisting of

(i) an inhibitor of respiration at cytochrome complex III, such as amethoxyacrylate type fungicide, for example, azoxystrobin andkresoxim-methyl,

(ii) ziram

(iii) fluazinam

(iv) zarilamide

(v) chlorothalonil

(vi) propamocarb

(vii) folpet

(viii) fosetyl-aluminum or a fungitoxic metabolite thereof such asphosphorous acid,

(ix) a triphenyltin type fungicide such as fentin hydroxide and fentinacetate and

(x) a copper containing fungicide such as copper(I) sulfate, copper(II)sulfate, copper(II) sulfate pentahydrate, copper(I) oxide, copperhydroxide and Bordeaux mixture; and

(c) an agronomically acceptable carrier to the plant seed, to the plantfoliage or to the growth medium for the plant.

When R⁴ and R⁵ are different, optical enantiomers of the compounds ofthe present invention are possible due to the presence of an asymmetriccarbon atom linking R⁴ and R⁵. It is known that many biologically activecompounds have optical enantiomers, one of which is more active than theother. Similarly, for compounds used in the method of the presentinvention, the biological activity of one enantiomer may exceed that ofthe other enantiomer, as described in

“(C₁-C₄)alkyl” means a straight or branched alkyl group having one tofour carbon atoms per group and includes methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

“(C₂-C₄)alkenyl” means a straight or branched alkenyl group having twoto four carbon atoms per group and includes, for example, ethenyl,2-propenyl, 2-butenyl, 1-methylethenyl, 2-methyl-2-propenyl and thelike.

“(C₂-C₆)alkynyl” means a straight or branched alkynyl group having fromtwo to six carbons per group and includes, for example, ethynyl,2-propynyl, 2-butynyl and the like.

“Halo” means chloro, fluoro, bromo and iodo.

“(C₁-C₄)alkoxy” means a straight or branched alkoxy group having one tofour carbon atoms per group and includes, for example, methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy.

“Cyano” means a group having the structural formula -CN.

“Thiocyano” means a group having the structural formula -SCN.

“Isothiocyano” means a group having the structural formula -NCS.

Agronomically acceptable salts include, for example, metal salts such assodium, potassium, calcium and magnesium salts, ammonium salts such asisopropyl ammonium salts and trialkylsulfonium salts such astriethylsulfonium salts.

The first fungicidally active compound may be a single compound offormula (I) or, alternatively, may be a mixture of compounds of formula(I). Suitable compounds of formula (I) include, but are not limited to,

N-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide,

N-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-ethylbenzamide,

N-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-ethoxybenzamide,

N-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methoxybenzamide,

N-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-cyanobenzamide,and

N-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dibromo-4-methylbenzamide.

In a preferred embodiment, the first fungicidally active compound is

N-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide,

N-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dibromo-4-cyanobenzamideor a mixture thereof.

More preferably, the first fungicidally active compound is

N-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide.

Suitable compounds which function as the second fungicidally activecompound include, but are not limited to, azoxystrobin, kiesoxim-methyl,ziram, fluazinam, zarilamide, chlorothalonil, propamocarb, folpet,fosetyl-aluminum, phosphorous acidfentin hydroxide, fentin acetate,copper(I) sulfate, copper(II) sulfate, copper(II) sulfate pentahydrate,copper(I) oxide, copper hydroxide and Bordeaux mixture.

In a preferred embodiment, the second fungicidally active compound isselected from the group consisting of fluazinam, propamocarb, folpet,fosetyl-aluminum, phosphorous acid, copper hydroxide and copper(II)sulfate pentahydrate.

The method of the present invention may optionally further compriseapplication of other compounds having biological activity, for example,additional fungicidally active compounds or compounds having herbicidalactivity or insecticidal activity, to the plant seed, to the plantfoliage or to the growth medium for the plant.

The method of the present invention is useful for the control ofphytopathogenic fungi on crops and the first and second fungicidallyactive compounds may be applied as a soil fungicide, as a seedprotectant, as a foliar fungicide or as a combination thereof. In apreferred embodiment, the first and second fungicidally active compoundsare applied to a plant growth medium, to the plant seed or to plantfoliage at dosage rates of from 2 parts by weight (pbw) to 90 pbw, morepreferably from 5 pbw to 75 pbw, of the first fungicidally activecompound per 100 pbw of the combined amount of first and secondfungicidally active compounds and from 10 pbw to 98 pbw, more preferablyfrom 25 pbw to 95 pbw, of the second fungicidally active compound per100 pbw of the combined amount of first and second fungicidally activecompounds.

As a soil fungicide, the first and second fungicidally activecompositions can be incorporated in the soil or applied to the surfaceof the soil at a dosage rate of about 0.25 kg to 5 kg of the firstfungicidally active compound and from 0.25 kg to 5 kg of the secondfungicidally active compound per hectare.

As a seed protectant, the first and second fungicidally active compoundsare coated on seed at a dosage rate of about 0.5 kilograms (kg) to 5 kgof the first fungicidally active compound and from 0.5 kg to 5 kg of thesecond fungicidally active compound per 100 kg seed.

As a foliar fungicide, the first and second fungicidally activecompounds are applied to plant foliage at a dosage rate of from 0.01 kgper hectare to 5 kg per hectare of the first fungicidally activecompound, and a dosage rate of from 0.01 kg per hectare to about 5 kgper hectare of the second fungicidally active compound. In a preferredembodiment, the first fungicidally active compound is applied to plantfoliage at a dosage rate of from 0.05 kg per hectare to about 0.5 kg perhectare. In a preferred embodiment, the second fungicidally activecompound is applied to plant foliage at a dosage rate of 0.05 kg perhectare to 5.0 kg per hectare. The first and second fungicidally activecompounds can be applied to plant foliage as fungicidal sprays bymethods commonly employed, such as conventional high-gallonage hydraulicsprays, low-gallonage sprays, air-blast, aerial sprays and dusts. Whilethe dilution and rate of application will depend upon the type ofequipment employed, the method and frequency of application desired anddiseases to be controlled, the effective amount is typically from about0.1 kg to about 5.0 kg, p)referably 0.2 kg to 5.0 kg, of both the firstand second active compounds per hectare.

The first and second fungicidally active compounds may be appliedsimultaneously or sequentially.

In a preferred embodiment, the first and second fungicidally activecompounds are simultaneously applied to plant growth medium, the plantseed, plant foliage or a combination thereof as a composition comprisinga mixture of the first fungicidally active compound and secondfungicidally active compound. In the preferred embodiments, the mixtureincludes from 2 pbw to 90 pbw of a first fungicidally active compoundand from 10 pbw to 98 pbw of a second fungicidally active compound per100 pbw of the mixture.

In an alternative embodiment, the first and second fungicidally activecompounds are applied sequentially to the plant seed, plant foliage orplant growth medium, with application of the second-applied compoundfollowing application of the first-applied compound by up to 72 hours.The compounds may be applied in either order: either the firstfungicidally active compound followed by the second fungicidally activecompound or, alternatively, as application of the second fungicidallyactive compound followed by the first fungicidally active compound.

The method of the present invention is useful in controlling certainphytopathogenic fungi, particularly fungi of the class Oomycetes, andprovides high fungicidal activity and relatively low phytotoxicity. Themethod of the present invention is particularly effective in controllingOomycete fungi of the genera Phytophthora, Plasmopara, Peronospora,Albugo and Pseudoperonospora, and even more particularly against theorganisms of those genera that cause diseases such as late blight intomatoes and potatoes and downy mildew in grapes and other crops,including, for example, Phytophthora infestans, Plasmopara viticola andPseudoperonospora cubensis.

For each of the above disclosed purposes, the first and secondfungicidally active compounds can be used in the technical or pure formas prepared, as solutions or as formulations. The compounds are usuallytaken up in a carrier or are formulated so as to render them suitablefor subsequent use as fungicides. For example, the compounds can beformulated as wettable powders, dry powders, emulsifiable concentrates,dusts, granular formulations, aerosols, or flowable emulsionconcentrates. In such formulations, the compounds are extended with aliquid or solid carrier and, when dried, suitable surfactants areincorporated. It is usually desirable, particularly in the case offoliar spray formulations, to include adjuvants, such as wetting agents,spreading agents, dispersing agents, stickers, adhesives and the like inaccordance with agricultural practices. Such adjuvants commonly used inthe art can be found in McCutcheon's “Emulsifiers and Detergents”,McCutcheon's “Emulsifiers and Detergents/Functional Materials” andMcCutcheon's “Functional Materials” all published annually by McCutcheonDivision of MC Publishing Company (New Jersey).

In general, the compositions utilized in this invention can be dissolvedin appropriate solvents such as acetone, methanol, ethanol,dimethylformamide or dimethyl sulfoxide and such solutions extended withwater. The concentrations of the combined first and second activecompounds in the solution can vary from 1% to 90% with a preferred rangebeing 5% to 50%.

For the preparation of emulsifiable concentrates, the compositions usedin the invention can be dissolved in suitable organic solvents or amixture of solvents, together with an emulsifying agent which permitsdispersion of the first and second active compounds in water. Theconcentration of the combined first and second active compounds inemulsifiable concentrates is usually 10% to 90% and in flowable emulsionconcentrates, this can be as high as 75%. Wettable powders suitable forspraying, can be prepared by admixing the composition with a finelydivided solid, such as clays, inorganic silicates and carbonates, andsilicas and incorporating wetting agents, sticking agents, and/ordispersing agents in such mixtures. The concentration of the combinedfirst and second active compounds in such formulations is usually in therange of 20% to 98%, preferably 40% to 75%.

Dusts are prepared by mixing the composition of the present invention,or salts and complexes thereof, with finely divided inert solids whichcan be organic or inorganic in nature. Inert materials useful for thispurpose include botanical flours, silicas, silicates, carbonates andclays. One convenient method of preparing a dust is to dilute a wettablepowder with a finely divided carrier. Dust concentrations containing 20%to 80% of the combined first and second active compounds are commonlymade and are subsequently diluted to 1% to 10% use concentration.

The method of the present invention, wherein an N-acetonylbenzamide anda selected second fungicidally active compound are applied to plantseed, plant foliage or to a plant growth medium, unexpectedly provideshigher fungicidal activity than the same compounds used separately.

The results provided by the mixtures were compared with the predictedresults that were calculated using the formula set forth by S. R. Colbyin Weeds 1967, 15, 20-22 (“Colby's Formula”) from the results obtainedusing each of the compounds individually. The predicted results are alsoprovided in the following Examples. These examples, tables andexperimental procedures are provided for guidance to the practitionerand are not meant to limit the scope of the invention which is definedby the claims.

EXAMPLE 1 Test to Control Phytophthora Capsici UsingN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide(Compound A) and Phosphorous Acid (Compound C)

A dilution series of Compound A was prepared in dimethylsulfoxide (DMSO)and a dilution series of Compound C was prepared in sterile water.Aliquots of each were added to 25 ml of molten potato dextrose agar at50° C. to give the appropriate concentrations shown in the table below.Immediately after adding the compound(s), the molten agar was pouredinto 9-cm diameter petri plates and allowed to harden. The finalconcentration of DMSO in all plates was 0.25%. Control plates containedDMSO but neither compound. Plates were inoculated in the center with 1μl of a suspension of Phytophthora capsici (ATCC 15399, obtainable fromthe American Type Culture Collection, Rockville, Md., U.S.A) zoosporescontaining 5×10⁵ zoospores per milliliter. Three replicate plates wereused for each treatment. Fungal colony diameters were measured aftergrowth for 7 days at 25° C., and two measurements were taken from eachplate. Inhibition of growth was calculated by comparing growth in thetreatments with compound A and/or C with growth in the controls. Degreeof inhibition (Observed) is expressed as a percentage in Table 1 below.The predicted % inhibition in treatments containing both A and C wascalculated using the Colby Formula.

TABLE 1 Control of Phytophthora capsici Compound A Compound CConcentration Concentration % Inhibition % Inhibition ppm ppm (Observed)(Predicted) 0 70 48.3 0 100 72.1 0.2 0 34.1 0.3 0 52.8 0.2 70 75.4 65.90.3 70 77.3 75.6 0.2 100 88.1 81.6 0.3 100 91.1 86.8

EXAMPLE 2 Test to Control Phytophthora Capsici UsingN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide(Compound A) and CuSO₄.5H₂O (Compound D)

The test protocol followed was the same as described in Example 1 andthe results reported in Table 2.

TABLE 2 Control of Phytophthora capsici Compound A Compound DConcentration Concentration % Inhibition % Inhibition ppm ppm (Observed)(Predicted) 0 100 15.6 0 200 47.0 0 300 59.2 0.1  0 21.6 0.2  0 31.0 0.3 0 44.0 0.1 100 49.4 33.8 0.2 100 60.9 41.8 0.3 100 68.3 52.7 0.1 20084.7 58.4 0.2 200 98.6 63.4 0.3 200 100 70.3 0.1 300 l00 68.0 0.2 300100 71.8 0.3 300 100 77.2

EXAMPLE 2A In Vitro Test to Control Phytophthora Capsici UsingN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide(Compound A) and Copper Hydroxide (Compound D-1)

The test protocol followed was the same as described in Example 1 andthe results reported in Table 2A.

TABLE 2A Control of Phytophthora capsici Compound A Compound D-1Concentration Concentration % Inhibition % Inhibition ppm ppm (Observed)(Predicted) 0 60 15.7 0 80 34.3 0 100 45.5 0.02 0 21.5 0.04 0 36.8 0.080 48.5 0.12 0 54.7 0.02 60 54.2 33.8 0.04 60 60.2 46.7 0.08 60 66.1 56.60.12 60 69.5 61.8 0.02 80 76.6 48.4 0.04 80 77.8 58.5 0.08 80 81.5 66.20.12 80 91.8 70.2 0.02 100 89.2 57.2 0.04 100 91.5 65.6 0.08 100 91.871.9 0.12 100 94.3 75.3

EXAMPLE 3N-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide(Compound A)+Fosetyl-aluminum (Compound E) Combination Study

Two trials were conducted with the combination of fosetyl-aluminum andN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamideto evaluate the potential benefits of combinations of the two products.

The first trial was conducted to determine the appropriate rates for usein a combination of the two products.

Ratios where synergism was observed are 1:2.25, 1:4.5, 1:9, 1:18 and1:36.

EXAMPLE 3aN-[3′-(1′chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide+Fosetyl-aluminumCombination Study—Preliminary Application Rate Study

Two to three week old Bush Champion cucumbers and 2 week old Patiotomatoes were sprayed with the fungicidal compounds as protectantsprays. The plants were inoculated with cucumber downy mildew (CDM),Pseudoperonospora cubensis, and tomato late blight (TLB), Phytophthorainfestans, one day after spraying.

N-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamidewas extremely effective against the tomato late blight fungus in thistest.N-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamidealone at all rates tested gave 95% control or better. Since excellentresults were observed withN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamideat the rates tested, no synergism could be detected.

Cucumber downy mildew control withN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamideranged from 63 to 82%. There was a suggestion of synergism at somerates. The data suggested that theN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamiderates should be lowered and the trial repeated.

Using the Colby equation, E=X+Y−XY/100, results suggest that ratios or1:2.25 to 1:4.5 were potentially synergistic. The results of thecalculations are recorded in CDM calc. column as shown in Table 3a.

TABLE 3a Control of CDM and TLB CDM obs. CDM calc. TLB obs. Treatment kgai/ha % Control % Control % Control None 0 0 Cmpd. E 0.112 28 30.9 ″0.225 35 14.3 ″ 0.45 54 57.1 ″ 0.9 77 54.8 Cmpd. A 0.0125 63 97.1 Cmpd.A + 0.0125 + 0.112  55 73.4 94.8 Cmpd. E Cmpd. A + 0.0125 + 0.225  7075.9 90 Cmpd. E Cmpd. A + 0.0125 + 0.45  69 83 93.8 Cmpd. E Cmpd. A +0.0125 + 0.9   81 81 92.3 Cmpd. E Cmpd. A 0.025 70 96.7 Cmpd. A +0.025 + 0.112 60 78.4 97.6 Cmpd. E Cmpd. A + 0.025 + 0.225 71 80.5 97.1Cmpd. E Cmpd. A + 0.025 + 0.45  81 86.2 92.9 Cmpd. E Cmpd. A + 0.025 +0.9  85.8 93.1 95.2 Cmpd. E Cmpd. A 0.05 82 96.7 Cmpd. A +  0.05 + 0.11261 87 95.7 Cmpd. E Cmpd. A +  0.05 + 0.225 76 88.6 96.7 Cmpd. E Cmpd.A + 0.05 + 0.45 89 91.7 96.1 Cmpd. E Cmpd. A + 0.05 + 0.9  87.8 95.996.7 Cmpd. E Cmpd. A 0.1 72 97.1 Cmpd. A +  0.1 + 0.112 71 79.8 98.6Cmpd. E Cmpd. A +  0.1 + 0.225 87 81.8 97.6 Cmpd. E Cmpd. A +  0.1 +0.45 89.6 87.1 99 Cmpd. E Cmpd. A + 0.1 + 0.9 93.6 93.6 96.7

EXAMPLE 3bN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide+Fosetyl-aluminumCombination Study—Second Application Rate Study

As a result of the initial test, a second test was conducted against CDMwith lower rates ofN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide.Results with the adjusted rates confirmed the previous test with thehigher doses and indicated synergism at additional rates. There was verystrong synergism with some rates. Ratios were from 1:2.25 to 1:36. Theresults are reported in Table 3b. Specific ratios where synergism wasobserved were 1:2.25, 1:4.5, 1:9, 1:18 and 1:36.

TABLE 3b Control of CDM CDM obs. CDM calc. Treatment kg ai/ha % Control% Control None 0 Cmpd. E 0.225 14 Cmpd. E 0.45 33 Cmpd. E 0.9 41 Cmpd. A0.006 22 Cmpd. A + Cmpd. E 0.006 + 0.225 26 32.9 Cmpd. A + Cmpd. E0.006 + 0.45  49 47.7 Cmpd. A + Cmpd. E 0.006 + 0.9  54 54 Cmpd. A 0.02514 Cmpd. A + Cmpd. E 0.025 + 0.225 45 26 Cmpd. A + Cmpd. E 0.025 + 0.45 51 42.4 Cmpd. A + Cmpd. E 0.025 + 0.9  57 49.3 Cmpd. A 0.1 22 Cmpd. A +Cmpd. E  0.1 + 0.225 47 32.9 Cmpd. A + Cmpd. E  0.1 + 0.45 48 47.7 Cmpd.A + Cmpd. E 0.1 + 0.9 60 54

EXAMPLE 4N-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide(Compound A)+Propamocarb (Compound F) Tests Against TLB and CDM

Cucumber downy mildew and tomato late blight were effectively controlledwith different combinations ofN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamideand propamocarb.

Three week old Patio variety tomato and Busch Champion cucumber plantswere sprayed with the fungicide rates listed in Tables 4a and 4b. Oneday following application, the plants were inoculated with spore30-40×10⁴ spores/ml suspensions of the respective diseases. The plantswere incubated in mist cabinets for twenty-four hours and then placed incontrol temperature chambers for the duration of the experiment.

Visual assessments of disease infection was conducted and thetransformed to percent control values. The data in Tables 4a and 4bsuggest strong levels of synergism with the combinations. Ratios ofN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamideto propamocarb ranged from 1:1 to 1:42. Synergism was seen at theratios: 1:42, 1:21, 1:10.5, 1:5, 1:2.5 and 1:1.

TABLE 4a Tomato Late Blight Control % Control % Control Treatment Kgai/ha Observed Calculated Cmpd. F 0.063 0 0.125 3 0.25 17 Cmpd. A 0.00623 0.012 20 0.025 36 Cmpd. A + Cmpd. F 0.006 + 0.063 31 23 0.006 + 0.12537 27 0.006 + 0.25  60 36 Cmpd. A + Cmpd. F 0.012 + 0.063 42 20 0.012 +0.125 34 22 0.012 + 0.25  47 34 Cmpd. A + Cmpd. F 0.025 + 0.063 37 360.025 + 0.125 50 38 0.025 + 0.25  54 47

TABLE 4a Tomato Late Blight Control % Control % Control Treatment Kgai/ha Observed Calculated Cmpd. F 0.063 0 0.125 3 0.25 17 Cmpd. A 0.00623 0.012 20 0.025 36 Cmpd. A + Cmpd. F 0.006 + 0.063 31 23 0.006 + 0.12537 27 0.006 + 0.25  60 36 Cmpd. A + Cmpd. F 0.012 + 0.063 42 20 0.012 +0.125 34 22 0.012 + 0.25  47 34 Cmpd. A + Cmpd. F 0.025 + 0.063 37 360.025 + 0.125 50 38 0.025 + 0.25  54 47

EXAMPLE 5aN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide(Compound A)+Folpet (Compound G) Tests Against CDM

The results in the accompanying Table 5a are forN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamideand folpet. The test was conducted as using the standard protocol(Example 3a) for cucumber downy mildew. Treatments were evaluated as a3-day residual application.

Synergism was observed at the following ratios ofN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamideto folpet for CDM disease: 1:4.5, 1:9 and 1:18. The results are reportedin Table 5a.

TABLE 5a Cucumber Downy Mildew Control Number of % Control % ControlTreatment Kg ai/ha Infection Sites Observed Calculated Cmpd. G 0.113 1628.8 0.225 22.2 0 0.45 19.2 8.5 Cmpd. A 0.025 5.4 74.3 0.05 3.2 84.8 0.10.4 98.1 Cmpd. A + 0.025 + 0.225 3.6 82.9 74.3 Cmpd. G 0.025 + 0.45  2.289.5 76.5 Cmpd. A +  0.05 + 0.225 2.2 89.5 84.8 Cmpd. G 0.05 + 0.45 2.289.5 84.8

EXAMPLE 5bN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide(Compound A)+Folpet (Compound G) Tests Against PLB

Three to four week old potato seedlings were sprayed with a series ofdoses of folpet andN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide. Individual treatments and combination treatments werecompared for biological efficacy against Phytophthora infestans onpotatoes (PLB). Fungicide solutions were sprayed and inoculated one dayafter the application. Inoculation was completed with a spore suspensionof 30-40×10⁴ spores/ml. The plants were placed in a misting cabinet for24 hours. Following the infection period, plants were placed in aconstant temperature chamber for the duration.

One day following application, the plants were inoculated with sporesuspensions of the respective diseases. The plants were incubated inmist cabinets for twenty-four hours and then placed in controltemperature chambers for the duration of the experiment.

Disease pressure was very high in this test as is evidenced by theexceptionally low level of control expressed by the individualtreatment. However the combinations were more active than either of thefungicides used alone.

N-[3′(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamideand folpet at ratios of 1:2.25, 1:4.5 and 1:9 exhibited synergism inthis test. The results are reported in Table 5b.

TABLE 5b Potato Late Blight Control % Control % Control Treatment Kgai/ha Observed Calculated Cmpd. G 0.225 0 0.45 3.5 Cmpd. A 0.05 12 0.1016 Cmpd. A + Cmpd. G  0.05 + 0.225 32 12 0.05 + 0.45 20 15 Cmpd. A +Cmpd. G  0.10 + 0.225 21 16 0.10 + 0.45 39 19

EXAMPLE 6aN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide(Compound A)+Fluazinam (Compound H) Test Against TLB

The results in the accompanying Table 6a are forN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamideand fluazinam against TLB. The test was conducted as using the standardprotocol (Example 3a) for tomato late blight. Treatments were applied asone day protectant applications.

Synergism was observed at the 1:5 ratio ofN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamideto fluazinam. The results are reported in Table 6a.

TABLE 6a Tomato Late Blight Control % Control % Control Treatment Kgai/ha % Infection Observed Calculated Cmpd. H 0.125 64 20 Cmpd. A 0.02513.2 84 Cmpd. A + 0.025 + 0.125 6.2 92 87.6 Cmpd. H

EXAMPLE 6bN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide(Compound A)+Fluazinam (Compound H) Test Against GDM

An example of synergism was observed with fluazinam in a test againstgrape downy mildew, Plasmopara viticola.

Tissue culture produced from Delaware grapes were sprayed with thefungicides. Inoculation with grape downy mildew (GDM) spores having aconcentration of 40,000 spores ml was conducted 1 day after theapplication. Plants were placed in a mist chamber for 24 hrs and thenmoved to a control temperature chamber for the remainder of the testperiod. The results are reported in Table 6b.

TABLE 6b Grape Downy Mildew Control % Control % Control Treatment Kgai/ha Observed Calculated Cmpd. H 0.006 52 Cmpd. A 0.006 22 Cmpd. A +Cmpd. H 0.006 + 0.006 76 63

It is to be understood that changes and variations in this invention maybe made without departing from the spirit and scope of this invention asdefined by the appended claims.

We claim:
 1. A fungicidal composition comprising synergisticfungicidally effective amounts of (a) a first fungicidally activecompound which isN-[3′-(1′-chloro-3′-methyl-2′-oxopentan)]-3,5-dichloro-4-methylbenzamide,(b) a second fungicidally active compound compound which is copperhydroxide, and (c) an agronomically acceptable carrier.
 2. A method forcontrolling phytopathogenic fungi on a plant comprising the applicationof a synergistic fungicidally effective amount of the composition ofclaim
 1. 3. The method of claim 2 wherein the phytopathogenic fungibelong to the class Oomycetes and are of the genera Phytophthora,Plasmopara, Peronospora, Albugo or Pseudoperonospora.
 4. The method ofclaim 2 wherein the plant is a potato plant, a tomato plant, a grapeplant or a cucumber plant.
 5. The method of claim 2 wherein the amountsof the first and second fungicidally active compounds applied comprisefrom 2 parts by weight to 90 parts by weight of the first fungicidallyactive compound and from 10 parts by weight to 98 parts by weight of thesecond fungicidally active compound per 100 parts by weight of thecombined amount of the first and second fungicidally active compounds.